Fungicidal mixtures based on morpholine or piperidine derivatives and oxime ether derivatives

ABSTRACT

Fungicidal mixtures, comprising as active components 
 
a) a morpholine or piperidine derivative I selected from the group of the compounds Ia, Ib, Ic and Id  
                 
 
b) compounds of the formula II  
                 
 
where the substituents X 1  to X 5  and R 1  to R 4  are as defined below: 
         X 1  is C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy or halogen;    X 2  to X 5  are, independently of one another, hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;    R 1  is C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkyl-C 3 -C 7 -cycloalkyl, C 1 -C 4 -alkyl-C 3 -C 7 -cycloalkenyl, where these radicals may carry substituents selected from the group consisting of halogen, cyano and C 1 -C 4 -alkoxy,    R 2  is a phenyl radical or a 5- or 6-membered saturated or unsaturated heterocyclyl radical having at least one heteroatom selected from the group consisting of N, O and S, where the cyclic radicals may have one to three substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxy-C 2 -C 4 -alkenyl, C 1 -C 4 -alkoxy-C 2 -C 4 -alkynyl,    R 3  and R 4  are, independently of one another, hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, N-C 1 -C 4 -alkylamino, C 1 -C 4 -haloalkyl or C 1 -C 4 -haloalkoxy in a synergistically effective amount are described.

The present invention relates to fungicidal mixtures for controllingharmful fungi and to methods for controlling harmful fungi using suchmixtures.

WO 97/40673 provides fungicidal mixtures which, inter alia, compriseactive compounds of the formulae Ia, Ib and/or Ic in addition to otherfungicidally active compounds from the group of the oxime ethers and/orthe carbamates.

Other fungicidal mixtures which comprise active compounds of theformulae Ia to Ic are disclosed in EP-A 797386, WO 97/06681, EP-B425857, EP-B 524496, EP-A 690792, WO 94/22308 and EP-B 645087.

Brighton Crop Protection Conference 1996, Pests and Diseases, pp. 47-52discloses the active compound of the formula Id:

DE 19722223 describes mixtures of compounds of the formula II and ofactive compounds from the class of the strobilurins.

It is an object of the present invention to provide other particularlyeffective mixtures for controlling harmful fungi and, in particular, forcertain indications.

We have found that this object is surprisingly achieved with a mixturewhich, as active compounds, comprises morpholine or piperidinederivatives of the formula I defined at the outset and, as furtherfungicidally active component, at least one fungicidally active compoundof the formula II

where the substituents X¹ to X⁵ and R¹ to R⁴ are as defined below:

-   -   X¹ is C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or halogen    -   X² to X⁵ are, independently of one another, hydrogen, halogen,        C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy;    -   R¹ is C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,        C₁-C₄-alkyl-C₃-C₇-cycloalkyl, where these radicals may carry        substituents selected from the group consisting of halogen,        cyano and C₁-C₄-alkoxy,    -   R² is a phenyl radical or a 5- or 6-membered saturated or        unsaturated heterocyclyl radical having at least one heteroatom        selected from the group consisting of N, O and S, where the        cyclic radicals may have one to three substituents selected from        the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₂-C₄-alkenyl,        C₁-C₄-alkoxy-C₂-C₄-alkynyl,    -   R³ and R⁴ are, independently of one another, hydrogen,        C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, N-C₁-C₄-alkylamino,        C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy    -   in a synergistically effective amount.

The mixtures according to the invention act synergistically, and theyare therefore particularly Suitable for controlling harmful fungi and,in particular, powdery mildew fungi.

In the context of the present invention, halogen is fluorine, chlorine,bromine and iodine and in particular fluorine, chlorine and bromine.

The term “alkyl” includes straight-chain and branched alkyl groups.These are preferably straight-chain or branched C₁-C₁₂-alkyl groups andin particular C₁-C₆-alkyl groups. Examples of alkyl groups are alkyl,such as, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl [lacuna] 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group which is defined as above and is partiallyor fully halogenated by one or more halogen atoms, in particular byfluorine and chlorine. Preferably, there are 1 to 3 halogen atomspresent, and particular preference is given to the difluoromethane [sic)and the trifluoromethyl group.

The alkenyl group includes straight-chain and branched C₂-C₆-alkenylgroups. Examples of alkenyl groups are 2-propenyl, 2-butenyl, 3-butenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl,4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, inparticular 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and3-methyl-2-pentenyl.

The alkenyl group may be partially or fully halogenated by one or morehalogen atoms, in particular by fluorine and chlorine. It has preferably1 to 3 halogen atoms.

The alkynyl group includes straight-chain and branched C₃-C₆-alkynylgroups. Examples of alkynyl groups are 2-propynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl,4-alkynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and1-ethyl-1-methyl-2-propynyl.

The C₁-C₄-alkylene-C₃-C₇-cycloalkyl group is a C₃-C₇-cycloalkyl group,such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which isattached via a C₁-C₄-alkylene radical.

Suitable substituents R² are, in addition to phenyl (unsubstituted orsubstituted), in particular thienyl, pyrazolyl, pyrrolyl, imidazolyl,thiazolyl, furyl, pyridazinyl and pyrimidinyl. Preferred substituents atthese ring systems are halogen (in particular F and Cl), C₁-C₄-alkoxy(in particular methoxy) and C₁-C₄-alkyl (in particular methyl, ethyl).The number of the ring substituents can be from 1 to 3 and is inparticular 1 or 2. Particular preference is given to phenyl orsubstituted phenyl, thienyl, thienyl-C₁-C₄-alkyl, pyrazolyl andpyrazol-C₁-C₄-alkyl.

The substituents R³ and R⁴ are C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylthio, N-C₁-C₄-alkylamino, C₁-C₄-haloalkyl orC₁-C₄-haloalkoxy. Preferred substituents R³ and R⁴ are hydrogen, F, Cl,methyl, ethyl, methoxy, thiomethyl and N-methylamino. R³ and R⁴ togethermay also form a grouping ═O.

The morpholine or piperidine derivatives I (Ia: common name:Fenpropimorph, U.S. Pat. No. 4,202,894; Ib: common name: Fenpropidin,U.S. Pat. No. 4,202,894; Ic: common name: Tridemorph, DE-A 11 64 152),their preparation and their action against harmful fungi are known, andthey are commercially available products.

The compounds of the formula II and processes for their preparation aredescribed in WO-A 96/19442 and in the earlier applications DE 1 9741098.7 and 1 97 41099.5.

Among the compounds of the formula II, preference is given to thosewhere X¹ is a C₁-C₄-haloalkyl, in particular a trifluoromethyl group, aC₁-C₄-haloalkoxy, in particular a difluoromethoxy or trifluoromethoxygroup or a halogen, in particular chlorine and X² and X³ are a hydrogenatom or a halogen group, in particular a hydrogen atom. X⁴ and X⁵ arepreferably hydrogen, halogen (in particular Cl or F), C₁-C₄-alkoxy (inparticular methoxy or ethoxy), C₁-C₄-haloalkyl (in particulartrifluoromethyl) or C₁-C₄-haloalkoxy (in particular trifluoromethoxy).

Preferred substituents R¹ are C₁-C₄-alkyl (methyl, ethyl, n- andisopropyl and t-butyl), C₁-C₄-alkylene-C₃-C₇-cycloalkyl, C₁-C₄-alkenyl(in particular ethenyl, propenyl and butenyl, which may be substituted,in particular by halogen (preferably Cl)), propynyl, cyanomethyl andmethoxymethyl. Among the C₁-C₄-alkylene-C₃-C₇-cycloalkyl substituents,methylene-substituted compounds, in particular methylenecyclopropyl,methylenecyclopentyl, methylenecyclohexyl and methylenecyclohexenyl, areparticularly preferred. The rings in these substituents may besubstituted, preferably by halogen.

Suitable substituents R² are, in addition to phenyl (unsubstituted orsubstituted), in particular thienyl, pyrazolyl, pyrrolyl, imidazolyl,thiazolyl, furyl, pyridazinyl and pyrimidinyl. Preferred substituents atthese ring systems are halogen (in particular F and Cl), C₁-C₄-alkoxy(in particular methoxy) and C₁-C₄-alkyl (in particular methyl, ethyl).The number of the ring substituents can be from 1 to 3 and is inparticular 1 or 2. Particular preference is given to phenyl orsubstituted phenyl.

Preferred compounds of the formula II are shown in the tables of WO96/019442, which has already been mentioned. Among these compounds, inturn, particular preference is given to the compounds listed in Table 1below (R³ and R⁴ are each hydrogen). TABLE 1 No. X¹ X² X³ X⁴ X⁵ R¹ R²II.1 CF₃ H H H H ethyl Ph-4-OMe II.2 CF₃ H H H H methyl Ph-4-OMe II.3CF₃ H H H H —CH₂-cPr 2-thienyl II.4 CF₃ H H H H —CH₂-cPr 3-thienyl II.5CF₃ H H H H —CH₂-cPr Ph-2,4-F₂ II.6 CF₃ H H H H —CH₂-cPr Ph-2-F II.7 CF₃H H H H —CH₂-cPr Ph-2-F-4-OMe II.8 CF₃ H H H H —CH₂-cPr Ph-3-Me II.9 CF₃H H H H —CH₂-cPr Ph-3-Me-4-OMe II.10 CF₃ H H H H —CH₂-cPr Ph-4-F II.11CF₃ H H H H —CH₂-cPr Ph-4-Me II.12 CF₃ H H H H —CH₂-cPr Ph-4-OMe II.13CF₃ H H H H —CH₂-cPr Ph II.14 CF₃ H H H H —CH₂—CH═CH₂ Ph II.15 CF₃ H H HH —CH₂—CH═CH₂ Ph-4-OMe II.16 CF₃ H H H H —CH₂—CH═CCl₂ Ph-4-OMe II.17 CF₃H H H F —CH₂—CH₃ Ph-4-OMe II.18 CF₃ H H H F —CH₂CH₃ Ph II.19 CF₃ H H H F—CH₃ Ph-4-OMe II.20 CF₃ H H H F —CH₂-cPr Ph II.21 CF₃ H H H F —CH₂-cPrPh-2-F II.22 CF₃ H H H F —CH₂-cPr Ph-2,4-F₂ II.23 CF₃ H H H F —CH₂-cPrPh-2-F-3-Me II.24 CF₃ H H H F —CH₂-cPr Ph-2-F-4-OMe II.25 CF₃ H H H F—CH₂-cPr Ph-3,5-Me₂ II.26 CF₃ H H H F —CH₂-cPr 3-methylpyrazol-1-ylII.27 CF₃ H H H F —CH₂-cPr 3-methyl-2-thienyl II.28 CF₃ H H H F —CH₂-cPr2-thienyl II.29 CF₃ H H H F —CH₂-cPr 3-thienyl II.30 CF₃ H H H F—CH₂—CHF₂ Ph-4-OMe II.31 CF₃ H H H F —CH₂—OCH₃ Ph-4-OMe II.32 CF₃ H H HF —CH₂—OCH₃ Ph II.33 CF₃ H H H F —CH₂CN Ph-4-Ome II.34 CF₃ H H H F—CH₂CN Ph II.35 CF₃ H H H F —CH₂—C═CH Ph II.36 CF₃ H H H F —CH₂—C═CHPh-4-OMe II.37 CF₃ H H H F —CH₂—C═CH Ph-2-F II.38 CF₃ H H H F —CH₂—C═CHPh-4-Me II.39 CF₃ H H H F —CH₂—C═CH 2-thienyl II.40 CF₃ H H H F—CH₂—C═CH Ph-2-F-4-OMe II.41 CF₃ H H H F i-propyl Ph II.42 CF₃ H H H Fn-butyl Ph II.43 CF₃ H H H F n-propyl Ph II.44 CF₃ H H H F t-butyl PhII.45 CF₃ H H H Cl —CH₃ II.46 CF₃ H H H Cl —CH₂CN Ph-4-OMe II.47 CF₃ H HH Cl —CH₂—OMe Ph-4-OMe II.48 CF₃ H H H Cl —CH₂-cPr Ph II.49 CF₃ H H H Cl—CH₂-cPr 3-methylpyrazol-1-yl II.50 CF₃ H H H Cl —CH₂-cPr 2-thienylII.51 CF₃ H H H Cl —CH₂-cPr Ph-2,4-F₂ II.52 CF₃ H H H Cl —CH₂—C═CHPh-4-OMe II.53 CF₃ H H H CF₃ —CH₃ Ph-4-OMe II.54 CF₃ H H H CF₃ —CH₂CH₂ClPh-4-OMe II.55 CF₃ H H H CF₃ —CH₂-cPr 2-thienyl II.56 CF₃ H H H CF₃—CH₂-cPr Ph-2-F-5-Me II.57 CF₃ H H H CF₃ —CH₂-cPr Ph-4-OMe II.58 CF₃ H HH CF₃ —CH₂-cPr Ph II.59 CF₃ H H H OCH₃ —CH₂CH₃ Ph-4-OMe II.60 CF₃ H H HOCH₃ —CH₂-cPr Ph-4-OMe II.61 CF₃ H H H OCH₃ —CH₂-cPr Ph II.62 CF₃ H H ClF —CH₂—CH₂Cl Ph II.63 CF₃ H H Cl F —CH₂—CH═CH₂ Ph-4-OMe II.64 CF₃ H H ClF —CH₂-cPr 2-thienyl II.65 CF₃ H H Cl F —CH₂-cPr Ph-2-F II.66 CF₃ H H ClF —CH₂-cPr Ph II.67 CF₃ H H Cl F —CH₂-cPr Ph-2-F-5-Me II.68 CF₃ H H ClCl —CH₂—CH═CH₂ Ph-4-OMe II.69 CF₃ H H Cl Cl —CH₂CH₂Cl Ph II.70 CF₃ H HCl Cl —CH₂CH₃ Ph-2-F-5-Me II.71 CF₃ H H Cl Cl —CH₂-cPr Ph-3,5-Me₂ II.72CF₃ H H SCH₃ F —CH₂-cPr Ph-4-OMe II.73 CF₃ H H OCH₃ F —CH₂-cPr Ph-4-OMeII.74 CF₃ H F H H —CH₂-cPr Ph II.75 CF₃ H F H H —CH₂—CH₃ Ph-4-OMe II.76CF₃ H H F F —CH₂CH₃ Ph II.77 CF₃ H H F F —CH₂—CH₂Cl Ph-2-F-5-Me II.78CF₃ H H F F —CH₂—OCH₃ Ph-4-OMe II.79 CF₃ H H F F —CH₂-cPr Ph II.80 CF₃ HH F F —CH₂-cPr 3-methylpyrazol-1-yl II.81 CF₃ H H F F —CH₂-cPr3-methyl-2-thienyl II.82 CF₃ H H F F —CH₂-cPr Ph-2-F-3-Me II.83 CF₃ H HF F —CH₂-cPr Ph-2-F-4-OMe II.84 CF₃ H H F F —CH₂-cPr Ph-2-F-5-Me II.85CF₃ H H F F —CH₂-cPr Ph-4-OMe II.86 CF₃ H H F F —CH₂-cPr Ph-4F II.87 CF₃H H F F i-propyl Ph-4-OMe II.88 CF₃ H H F F n-butyl Ph-4-OMe II.89 CF₃ HH F F —CH₂—C═CH Ph-4-OMe II.90 CF₃ H H CF₃ F —CH₃ Ph-4-OMe II.91 CF₃ H HCF₃ F —CH₂—CH═CH₂ Ph II.92 CF₃ H H CF₃ F —CH₂-cPr Ph II.93 CF₃ H H Cl Cl—CH₂-cHxe-3 Ph II.94 CF₃ H H F H —CH₂-cPr Ph-4-F II.95 CF₃ H H Cl Cl—CH₂-cHex Ph II.96 CF₃ H H H F —CH₂—SCH₃ Ph II.97 CF₃ H H H F —CH₂—SOCH₃Ph II.98 CF₃ H H H F —CH₂—SO₂CH₃ Ph II.99 CF₃ H H H F —CH₂—NHMe PhII.100 CF₃ H H H F CH₂—CONH₂ Ph II.101 CF₃ H H H F CH₂CON(CH₃)₂ Ph

In the table above, cPr is cyclopropyl, cHxe-n is cyclohexenyl which isunsaturated in position n, c-Hex is cyclohexyl and Ph is phenyl.

Particular preference is given to compounds II in which R¹ is a radicalCH₂-cPr and R² is an unsubstituted or substituted phenyl radical. Amongthese, in turn, preference is given to the compounds in which X⁴ and X5[sic) are halogen, preferably F.

Other preferred compounds of the formula II are shown in Tables 2 and 3below. TABLE 2 Compounds of the formula II′ (II′)

where the substituents are as defined below: No. X¹ R′ m.p. (° C.)II.102 H 4-CH₃—C₆H₄—CH₂ 86-88 II.103 H 4-F—C₆H₄—CH₂ 79-81 II.104 H4-Cl—C₆H₄—CH₂ 105-107 II.105 H 4-CH₃O—C₆H₄—CH₂ 73-76 II.106 H4-CF₃—C₆H₄—CH₂ II.107 5-F 4-CH₃—C₆H₄—CH₂ 87-90 II.108 5-F 4-F—C₆H₄—CH₂71-74 II.109 5-F 4-Cl—C₆H₄—CH₂ 85-87 II.110 5-F 4-CH₃O—C₆H₄—CH₂ 90-92II.111 5-F 4-CF₃—C₆H₄—CH₂ II.112 H 2-thienylmethyl 87-89 II.113 H3-thienylmethyl II.114 5-F 2-thienylmethyl 90-93 II.115 5-F3-thienylmethyl II.116 5-F 3-CH₃—C₆H₄—CH₂ 72-75 II.117 5-F 2-F—C₆H₄—CH₂73-76 II.118 5-F 4-CH₂FO—C₆H₄—CH₂ oil

TABLE 3 Compounds of the formula II″ (II″)

m.p. No. OX¹ X² R¹ R″ ° C. II.119 CHF₂ H C₂H₅ C₆H₅—CH₂ II.120 CHF₂ HC₂H₅ 4-CH₃O—C₆H₄—CH₂ II.121 CHF₂ H CH₂—CH═CH₂ C₆H₅—CH₂ II.122 CHF₂ HCH₂—C≡CH C₆H₅—CH₂ II.123 CHF₂ H CH₂—C≡CH 4-CH₃O—C₆H₄—CH₂ II.124 CHF₂ HcPr C₆H₅—CH₂ II.125 CF₃ H cPr C₆H₅—CH₂ II.126 CHF₂ H cPr 4-F—C₆H₄—CH₂75-77 II.127 CHF₂ H cPr 4-Cl—C₆H₄—CH₂ 81-83 II.128 CHF₂ H cPr4-CH₃O—C₆H₄—CH₂ 57-59 II.129 CHF₂ H cPr 4-CF₃—C₆H₄—CH₂ II.130 CHF₂ H cPr2-thienylmethyl oil II.131 CHF₂ H cPr 3-thienylmethyl oil II.132 CHF₂ HcPr pyrazolyl-1-methyl II.133 CHF₂ H cPr 4-CH₃—C₆H₄—CH₂ II.134 CHF₂ 5-FCH₂—CH═CH₂ C₆H₅—CH₂ II.135 CHF₂ 5-F CH₂—CH═CH₂ 4-CH₃—C₆H₄—CH₂ II.136CHF₂ 5-F CH₂—C≡CH C₆H₅—CH₂ II.137 CHF₂ 5-F CH₂—C≡CH 4-CH₃O—C₆H₄—CH₂II.138 CHF₂ 5-F cPr C₆H₅—CH₂ 62-65 II.139 CHF₂ 5-F cPr 4-F—C₆H₄—CH₂64-67 II.140 CHF₂ 5-F cPr 4-Cl—C₆H₄—CH₂ 72-75 II.141 CHF₂ 5-F cPr4-CH₃—C₆H₄—CH₂ 74-76 II.142 CHF₂ 5-F cPr 4-CH₃O—C₆H₄—CH₂ 79-81 II.143CHF₂ 5-F cPr 4-CF₃—C₆H₄—CH₂ II.144 CF₃ 5-F cPr C₆H₅—CH₂ II.145 CHF₂ 4-FcPr C₆H₅—CH₂ II.146 CHF₂ 4-F cPr 4-CH₃O—C₆H₄—CH₂ II.147 CHF₂ H cPr4-CH₃—C₆H₄—CH₂ 69-71

The physical data of these compounds and processes for their preparationare given in the already mentioned WO 96/19442, DE 197441098.7 and DE19741099.5.

The ratios of the compounds I and II can be varied within wide ranges;the active compounds are preferably employed in a ratio by weight in therange from 20:1 to 1:20, in particular 10:1 to 1:10.

When preparing the mixtures, it is preferred to employ the pure activeingredients I and II, to which further active ingredients againstharmful fungi or other pests, such as insects, arachnids or nematodes,or else herbicidal or growth-regulating active ingredients orfertilizers can be admixed.

The mixtures of the compounds I and II, or the compounds I and II usedsimultaneously, jointly or separately, exhibit outstanding activityagainst a wide range of phytopathogenic fungi, in particular from theclasses of the Ascomycetes, Basidiomycetes, Phycomycetes andDeuteromycetes. Some of them act systemically and can therefore beemployed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (e.g.cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine,wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinera (gray mold) in strawberries, vegetables,ornamentals and grapevines, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapevines, Pseudoperonospora species in hops andcucumbers, Alternaria species in vegetables and fruit, Mycosphaerellaspecies in bananas and Fusarium and Verticillium species.

They can furthermore be employed in the protection of materials (forexample the protection of wood), for example against Paecilomycesvariotii.

The compounds I and II can be applied simultaneously, that is eithertogether or separately, or successively, the sequence, in the case ofseparate application, generally not having any effect on the result ofthe control measures.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are, in particular in agriculturalcrop areas, from 0.01 to 10 kg/ha, preferably 0.1 to 5 kg/ha, inparticular 0.2 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to 2.5 kg/ha,preferably 0.01 to 10 kg/ha, in particular 0.05 to 5.0 kg/ha.

Correspondingly, in the case of the compounds II, the application 20rates are from 0.01 to 2 kg/ha, preferably 0.02 to 2 kg/ha, inparticular 0.02 to 1.0 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, inparticular 0.01 to 50 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II or of the mixtures of thecompounds I and II is effected by spraying or dusting the seeds, theplants or the soils before or after sowing of the plants, or before orafter plant emergence.

The fungicidal synergistic mixtures according to the invention or thecompounds I and II can be formulated for example in the form ofready-to-spray solutions, powder and suspensions or in the form ofhighly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for broadcasting orgranules, and applied by spraying, atomizing, dusting, broadcasting orwatering. The use form depends on the intended purpose; in any case, itshould ensure as fine and uniform as possible a distribution of themixture according to the invention.

The formulations are prepared in a known manner, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible also to use other organicsolvents as auxiliary solvents if water is used as the diluent. Suitableauxiliaries for this purpose are essentially: solvents such as aromatics(e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins(e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones(e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) andwater; carriers such as ground natural minerals (e.g. kaolins, clays,talc, chalk) and ground synthetic minerals (e.g. finely divided silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and dispersants such as lignosulfite waste liquors andmethylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, e.g. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol or tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxidecondensates, ethoxylated castor oil, polyoxyethylene alkyl ethers orpolyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitolesters, lignosulfite waste liquors or methylcellulose.

Powders [lacuna] materials for broadcasting and dusts can be prepared bymixing or jointly grinding the compounds I or II or the mixture of thecompounds I and II with a solid carrier.

Granules (e.g. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active compound, or activecompounds, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials andfertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably 0.5 to 90% by weight, of one of the compounds I or II or ofthe mixture of the compounds I and II. The active compounds are employedin a purity of from 90% to 100%, preferably 95% to 100% (according toNMR spectrum or HPLC spectrum [sic]).

The compounds I or II, the mixtures, or the corresponding formulations,are applied by treating the harmful fungi, their habitat, or the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally effective amount of the mixture, or of the compounds Iand II in the case of separate application.

Application can be effected before or after infection by the harmfulfungi.

Examples of such preparations comprising the active compounds are:

-   -   I. A solution of 90 parts by weight of the active compounds and        10 parts by weight of N-methylpyrrolidone; this solution is        suitable for use in the form of microdrops;    -   II. A mixture of 20 parts by weight of the active compounds, 80        parts by weight of xylene, 10 parts by weight of the adduct of 8        to 10 mol of ethylene oxide to 1 mol of oleic acid        N-monoethanolamide, 5 parts by weight of the calcium salt of        dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of        40 mol of ethylene oxide to 1 mol of castor oil; a dispersion is        obtained by finely distributing the solution in water;    -   III. An aqueous dispersion of 20 parts by weight of the active        compounds, 40 parts by weight of cyclohexanone, 30 parts by        weight of isobutanol, 20 parts by weight of the adduct of 40 mol        of ethylene oxide to 1 mol of castor oil;    -   IV. An aqueous dispersion of 20 parts by weight of the active        compounds, 25 parts by weight of cyclohexanol, 65 parts by        weight of a mineral oil fraction of boiling point 210 to 280°        C., and 10 parts by weight of the adduct of 40 mol of ethylene        oxide to 1 mol of castor oil;    -   V. A mixture, ground in a hammer mill, of 80 parts by weight of        the active compounds, 3 parts by weight of the sodium salt of        diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the        sodium salt of a lignosulfonic acid from a sulfite waste liquor        and 7 parts by weight of pulverulent silica gel; a spray mixture        is obtained by finely distributing the mixture in water;    -   VI. An intimate mixture of 3 parts by weight of the active        compounds and 97 parts by weight of finely divided kaolin; this        dust comprises 3% by weight of active compound;    -   VII. An intimate mixture of 30 parts by weight of the active        compounds, 92 parts by weight of pulverulent silica gel and 8        parts by weight of paraffin oil which had been sprayed onto the        surface of this silica gel; this formulation imparts good        adhesion to the active compound;    -   VIII. A stable aqueous dispersion of 40 parts by weight of the        active compounds, 10 parts by weight of the sodium salt of a        phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by        weight of silica gel and 48 parts by weight of water; this        dispersion may be diluted further;    -   IX. A stable oily dispersion of 20 parts by weight of the active        compounds, 2 parts by weight of the calcium salt of        dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol        polyglycol ether, 20 parts by weight of the sodium salt of a        phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by        weight of a paraffinic mineral oil.

USE EXAMPLE

The synergistic activity of the mixtures according to the invention canbe demonstrated by the following experiments:

The active compounds, separately or together, are formulated as a 10%emulsion in a mixture of 63% by weight of cyclohexanone and 27% byweight of emulsifier, and diluted with water to the desiredconcentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The efficacy(W) is calculated-as follows using Abbot's formula:W−(1−α/β)·100

-   -   α corresponds to the fungal infection of the treated plants in %        and    -   β corresponds to the fungal infection of the untreated (control)        plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of the active compounds weredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.Colby's formula: E=x+y−x·y/100

-   -   E expected efficacy, expressed in % of the untreated control,        when using the mixture of the active compounds A and B at the        concentrations a and b    -   x efficacy, expressed in % of the untreated control, when using        active compound A at a concentration of a    -   y efficacy, expressed in % of the untreated control, when using        active compound B at a concentration of b.

Use Example 1 Activity Against Mildew of Wheat

Leaves of potted wheat seedlings cv. “Kanzler” were sprayed to runoffpoint with an aqueous preparation of active compound which was preparedfrom a stock solution comprising 10% of active compound, 63% ofcyclohexanone and 27% of emulsifier and, 24 h after the spray coatinghad dried on, dusted with spores of mildew of wheat (Erysiphe graminisforma specialis tritici). The test plants were subsequently placed inclimatized chambers at 20-24° C. and 60-90% relative atmospherichumidity for 7 days. The extent of the development of the infection onthe leaves was then determined visually.

The visually determined values for the percentage of infected leaf areaswere converted into efficacies as % of the untreated control. Anefficacy of 0 means the same degree of infection as in the untreatedcontrol, an efficacy of 100 means 0% infection. The expected efficaciesfor active compound combinations were determined using Colby's formula(Colby, S. R. “Calculating synergistic and antagonistic responses ofherbicide combinations”, Weeds, 15 (1967), 20-22) and compared with theobserved efficacies.

The components II used were the compounds II.79 and II.138 from Table 2.

The results of the tests are shown in Tables 1 and 2 below: TABLE 1Efficacy in % of the untreated Ex. Active compound Conc. in ppm control1C without (67% infected) 0 2C Compound II.79 1 55 0.25 55 3C CompoundII.138 0.6 65 4C Compound I.a 0.25 55 (common name: fenpropimorph) 5CCompound I.b 0.25 55 (common name: fenpropidin) 6C Compound I.c 1 0(common name: 0.25 0 tridemorph)

TABLE 2 Mixture according to the Observed Calculated Ex. invention(conc. in ppm) efficacy efficacy* 7 0.25 ppm Ia + 96 80 0.25 ppm II.79 81 ppm Ic + 1 ppm II.79 85 55 9 0.25 ppm Ic + 90 55 0.25 ppm II.79 100.25 ppm Ib + 93 80 0.25 ppm II.79 11 0.25 ppm Ia + 100 84 0.06 ppmII.138 12 0.25 ppm Ic + 96 65 0.06 ppm II.138 13 0.25 ppm Ib + 25 840.06 ppm II.138*Calculated using Colby's formula

The test results show that, for all mixing ratios, the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula.

1. A fungicidal mixture, comprising as active components a) a compoundof the formula Id

and b) one or more compounds of the formula II

where the substituents X¹ to X⁵ and R¹ to R⁴ are as defined below: X¹ isC₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or halogen; X² to X⁵ are,independently of one another, hydrogen, halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy, R¹ is C₁-C₄-alkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkyl-C₃-C₇-cycloalkyl, where theseradicals may carry substituents selected from the group consisting ofhalogen, cyano and C₁-C₄-alkoxy, R² is a phenyl radical or a 5- or6-membered saturated or unsaturated heterocyclyl radical having at leastone heteroatom selected from the group consisting of N, O and S, wherethe cyclic radicals may have one to three substituents selected from thegroup consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₂-C₄-alkenyl,C₁-C₄-alkoxy-C₂-C₄-alkynyl, R³ and R⁴ are, independently of one another,hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio,N-C₁-C₄-alkylamino, C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy in asynergistically effective amount.
 2. A fungicidal mixture as claimed inclaim 1, where in the one or more compounds II, R¹ is C₁-C₄-alkyl orC₁-C₄-alkylene-C₃-C₇-cycloalkyl.
 3. A fungicidal mixture as claimed inclaim 1, where in the one or more compounds II, R² is phenyl, thienyl,pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, furyl, pyridazinyl orpyrimidinyl, and these radicals may be substituted by halogen,C₁-C₄-alkoxy or C₁-C₄-alkyl.
 4. A fungicidal mixture as claimed in claim1, where in the one or more compounds II, R³ or R⁴ are independently ofone another hydrogen, fluorine, chlorine, methyl, ethyl, methoxy,thiomethyl or N-methyamino.
 5. A fungicidal mixture as claimed in claim1, where in the one or more compounds II, X¹ is halo-C₁-C₆-alkyl,halo-C₁-C₆-alkoxy or halogen.
 6. A fungicidal mixture as claimed inclaim 1, where in the one or more compounds II, X² or X³ are hydrogen orhalogen.
 7. A fungicidal mixture as claimed in claim 1, where in the oneor more compounds II, X⁴ is hydrogen, chlorine, fluorine, methoxy,ethoxy, trifluoromethyl or trifluoromethoxy.
 8. A fungicidal mixture asclaimed in claim 1, where in the one or more compounds II, X⁵ ishydrogen, chlorine, fluorine, methoxy, ethoxy, trifluoromethyl ortrifluoromethoxy.
 9. A fungicidal mixture as claimed in claim 1, whichis conditioned in two parts, where one part comprises the compound Id ina solid or liquid carrier and the other part comprises the one or morecompounds of the formula II in a solid or liquid carrier.
 10. A methodfor controlling harmful fungi, which comprises treating the fungi, theirhabitat or the materials, plants, seeds, soils, areas or spaces to beprotected against fungal attack with a fungicidal mixture as claimed inclaim 1, where the compound Id and the one or more compounds of theformula II can be applied simultaneously, that is either together orseparately, or successively.
 11. A fungicidal mixture as claimed inclaim 1, wherein in the one or more compounds of the formula II X¹ isC₁-C₄-haloalkyl or C₁-C₄-haloalkoxy; X² is hydrogen or C₁-C₄-alkyl; X³is hydrogen or C₁-C₄-alkyl; X⁴ is halogen; X⁵ is halogen; R¹ ismethylenecyclopropyl, methylenecyclopentyl, methylenecyclohexyl ormethylenecyclohexenyl; R² is phenyl which is optionally substituted byhalogen, C₁-C₄-alkoxy or C₁-C₄-alkyl; R³ and R⁴ are, independently ofone another, hydrogen or C₁-C₄-alkyl.
 12. The mixture defined in claim11, wherein R¹ is methylenecyclopropyl.
 13. The mixture defined in claim11, wherein R² is phenyl.
 14. The mixture defined in claim 11, whereinR³or R⁴is hydrogen.
 15. The mixture defined in claim 11, wherein R³ andR⁴ are hydrogen.
 16. The mixture defined in claim 1 1, wherein X² or X³is hydrogen.
 17. The mixture defined in claim 11, wherein X² and X³ arehydrogen.
 18. The mixture defined in claim 11, wherein X⁴ is chlorine orfluorine.
 19. The mixture defined in claim 11, wherein X⁵ is chlorine orfluorine.
 20. The mixture defined in claim 11, wherein X² is hydrogen;X³ is hydrogen; R¹ is methylenecyclopropyl; R² is phenyl; and R³ and R⁴are hydrogen.
 21. The mixture defined in claim 12, which is conditionedin two parts, wherein one part comprises the compound Id in a solid orliquid carrier and the other part comprises the one or more compounds ofthe formula II in a solid or liquid carrier.
 22. A method forcontrolling harmful fungi, which comprises treating the fungi, theirhabitat or the materials, plants, seeds, soils, areas or spaces to beprotected against fungal attack with the mixture defined in claim 12,where the compound Id and the one or more compounds of the formula IIare applied simultaneously, that is either together or separately, orsuccessively.
 23. The mixture defined in claim 11, wherein in the one ormore compounds of the formula II X¹ is trifluoromethyl ordifluoromethoxy; X² is hydrogen; X³ is hydrogen; X⁴ is chlorine orfluorine; X⁴ is chlorine or fluorine; R¹ is methylenecyclopropyl; R² isphenyl; and R³ and R⁴ are hydrogen.
 24. The mixture defined in claim 11,which comprises the compound Id and the one or more compounds of theformula II in a ratio by weight of from 20:1 to 1:20.
 25. The method ofclaim 22, wherein the compound Id and the one or more compounds of theformula II are applied in a ratio by weight of from 20:1 to 1:20. 26.The method of claim 22, wherein the mixture is applied in an amount offrom 0.0 1 to 10 kg/ha.
 27. The method of claim 22, wherein the mixtureis applied to seeds in an amount of from 0.001 to 250 g/kg.
 28. Themethod of claim 22, wherein the compound Id is applied in an amount offrom 0.01 to 2.5 kg/ha.
 29. The method of claim 22, wherein the one ormore compounds of the formula II is applied in an amount of from 0.01 to2 kg/ha